organic compounds

Acta Crystallographica Section E Orthorhombic, P21 21 21 Z=4

Structure Reports a = 7.1969 (5) Å Mo K radiation
b = 11.8023 (7) Å  = 0.09 mm 1
Online c = 15.3721 (8) Å T = 296 K
ISSN 1600-5368 V = 1305.71 (14) Å3 0.32  0.14  0.14 mm

Data collection
2,3-Dimethyl-N-[(E)-4-nitrobenzylidene]- Bruker Kappa APEXII CCD 13172 measured reflections
diffractometer 1917 independent reflections
aniline Absorption correction: multi-scan 1253 reflections with I > 2(I)
(SADABS; Bruker, 2005) Rint = 0.057
Tmin = 0.986, Tmax = 0.987
Muhammad Ilyas Tariq,a Shahbaz Ahmad,a M. Nawaz
Tahir,b* Muhammad Sarfaraza and Ishtiaq Hussaina Refinement
a
R[F 2 > 2(F 2)] = 0.047 174 parameters
Department of Chemistry, University of Sargodha, Sargodha, Pakistan, and wR(F 2) = 0.111 H-atom parameters constrained
b
Department of Physics, University of Sargodha, Sargodha, Pakistan S = 1.02
max = 0.12 e Å 3
Correspondence e-mail: dmntahir_uos@yahoo.com 1917 reflections
min = 0.14 e Å 3

Received 22 May 2010; accepted 23 May 2010

Key indicators: single-crystal X-ray study; T = 296 K; mean (C–C) = 0.003 Å;
R factor = 0.047; wR factor = 0.111; data-to-parameter ratio = 11.0.
In the title compound, C15H14N2O2, the aromatic rings are
oriented at a dihedral angle of 24.52 (5) . The dihedral angle
between the nitro group and its parent benzene ring is
9.22 (16) . In the crystal, molecules interact through aromatic
— stacking interactions [centroid–centroid separations =
3.8158 (14) and 3.9139 (14) Å].
Related literature
For structural systematics of related compounds, see: Harada
et al. (2004).
Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT
(Bruker, 2007); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009);
software used to prepare material for publication: WinGX (Farrugia,
1999) and PLATON.
The authors acknowledge the provision of funds for the
purchase of diffractometer and encouragement by Dr
Muhammad Akram Chaudhary, Vice Chancellor, University
of Sargodha, Pakistan.
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: HB5464).

References
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Experimental Harada, J., Harakawa, M. & Ogawa, K. (2004). Acta Cryst. B60, 578–588.
Crystal data Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
C15H14N2O2 Mr = 254.28

Acta Cryst. (2010). E66, o1561 doi:10.1107/S160053681001932X Tariq et al. o1561

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 supplementary materials

Acta Cryst. (2010). E66, o1561 [ doi:10.1107/S160053681001932X ]

2,3-Dimethyl-N-[(E)-4-nitrobenzylidene]aniline

M. I. Tariq, S. Ahmad, M. N. Tahir, M. Sarfaraz and I. Hussain

Comment

Torsional, vibration and central bond length of N-benzylideneanilines (Harada et al., 2004) has been studied for seven
compounds at different temperatures. The title compound (I, Fig. 1) is another example due to change of substitutions at
both phenyl rings for which the same study can be undertaken. The title compound has been prepared for derivatization.

The molecules of (I) are essentially monomeric having no intra or inter-molecular H-bondings. The phenyl rings A
(C1—C6) and B (C10—C15) are planar with r. m. s. deviation of 0.0065 and 0.0022 Å respectively. The dihedral angle
between A/B is 24.52 (5)°. The nitro group C (O1/N2/O2) is oriented at 9.22 (16)° with the parent phenyl ring. It is to be
noted that the nitro substituated phenyl ring B has smaller bond lengths [1.365 (3)–1.387 (3) Å], whereas the 2,3-dimethyl
substituated ring has longer bond lengths 1.373 (3)—1.401 (3) Å. The value of C═N bond length at room temperature for
(I) is 1.262 (3) Å which is in compatible with the studies of Harada et al., 2004. The molecules are stabilized due to π—π
interactions between the centroids of phenyl rings with separation of 3.8158 (14) and 3.9139 (14) Å.

Experimental

Equimolar quantities of 2,3-dimethylaniline and 4-nitro benzaldehyde were refluxed in methanol for 15 minutes resulting in
yellow color precipitates. The contents of the flask were dried at room temperature and washed with methanol and ethanol,
respectively. The washed crude material affoarded yellow needles of (I) in the solution of diethyl ether at room temperature
by slow evaporation after 24 h.

Refinement

In the absence of anomalous scattering, all Friedal pairs were merged. Although all H-atoms were appeared in Fourier
difference map but positioned geometrically (C–H = 0.93–0.96 Å) and refined as riding with Uiso(H) = xUeq(C), where x
=1.2 for aryl C–H and x = 1.5 methyl H-atoms.

Figures

Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level.

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2,3-Dimethyl-N-[(E)-4-nitrobenzylidene]aniline

Crystal data
C15H14N2O2 F(000) = 536
Mr = 254.28 Dx = 1.294 Mg m−3
Orthorhombic, P212121 Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab Cell parameters from 1334 reflections
a = 7.1969 (5) Å θ = 2.1–25.4°
b = 11.8023 (7) Å µ = 0.09 mm−1
c = 15.3721 (8) Å T = 296 K
V = 1305.71 (14) Å3 Needle, yellow
Z=4 0.32 × 0.14 × 0.14 mm

Data collection
Bruker Kappa APEXII CCD
1917 independent reflections
diffractometer
Radiation source: fine-focus sealed tube 1253 reflections with I > 2σ(I)
graphite Rint = 0.057
Detector resolution: 7.40 pixels mm-1 θmax = 28.6°, θmin = 2.2°
ω scans h = −8→9
Absorption correction: multi-scan
k = −15→15
(SADABS; Bruker, 2005)
Tmin = 0.986, Tmax = 0.987 l = −20→20
13172 measured reflections

Refinement
Primary atom site location: structure-invariant direct
Refinement on F2 methods
Least-squares matrix: full Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring
R[F2 > 2σ(F2)] = 0.047 sites
wR(F2) = 0.111 H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0482P)2 + 0.0883P]
S = 1.02
where P = (Fo2 + 2Fc2)/3
1917 reflections (Δ/σ)max < 0.001
174 parameters Δρmax = 0.12 e Å−3
0 restraints Δρmin = −0.14 e Å−3

Special details
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the
variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and tor-
sion angles

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Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, convention-
al R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-
factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
O1 0.1409 (4) −0.19301 (18) 0.70198 (14) 0.0997 (9)
O2 0.1083 (4) −0.06237 (19) 0.79842 (12) 0.0941 (9)
N1 0.1128 (3) 0.34130 (16) 0.47092 (11) 0.0485 (7)
N2 0.1253 (3) −0.0943 (2) 0.72311 (16) 0.0684 (9)
C1 0.1231 (3) 0.42218 (18) 0.40278 (13) 0.0457 (7)
C2 0.1509 (3) 0.5351 (2) 0.42653 (14) 0.0488 (8)
C3 0.1581 (4) 0.61833 (19) 0.36160 (15) 0.0549 (8)
C4 0.1353 (4) 0.5864 (2) 0.27595 (17) 0.0624 (10)
C5 0.1052 (4) 0.4755 (2) 0.25272 (16) 0.0650 (10)
C6 0.0972 (4) 0.3935 (2) 0.31593 (14) 0.0550 (8)
C7 0.1768 (4) 0.5654 (2) 0.52133 (14) 0.0679 (10)
C8 0.1878 (5) 0.7409 (2) 0.38401 (19) 0.0820 (13)
C9 0.1573 (4) 0.23940 (19) 0.45751 (14) 0.0495 (8)
C10 0.1434 (3) 0.15342 (18) 0.52625 (14) 0.0448 (7)
C11 0.1832 (3) 0.04156 (19) 0.50760 (15) 0.0525 (8)
C12 0.1753 (4) −0.0397 (2) 0.57139 (15) 0.0551 (9)
C13 0.1287 (3) −0.0075 (2) 0.65402 (14) 0.0500 (8)
C14 0.0878 (3) 0.1021 (2) 0.67504 (15) 0.0523 (8)
C15 0.0953 (3) 0.18289 (19) 0.61064 (14) 0.0496 (8)
H4 0.14039 0.64145 0.23274 0.0748*
H5 0.09027 0.45617 0.19450 0.0779*
H6 0.07448 0.31854 0.30059 0.0659*
H7A 0.09112 0.62429 0.53696 0.1016*
H7B 0.30167 0.59128 0.53059 0.1016*
H7C 0.15399 0.49972 0.55663 0.1016*
H8A 0.18433 0.78558 0.33184 0.1229*
H8B 0.30655 0.74981 0.41166 0.1229*
H8C 0.09161 0.76571 0.42285 0.1229*
H9 0.20007 0.21822 0.40278 0.0594*
H11 0.21572 0.02105 0.45120 0.0630*
H12 0.20116 −0.11509 0.55867 0.0661*
H14 0.05543 0.12165 0.73165 0.0627*
H15 0.06802 0.25797 0.62382 0.0596*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
O1 0.131 (2) 0.0586 (12) 0.1094 (16) 0.0005 (15) 0.0004 (17) 0.0307 (12)
O2 0.1205 (19) 0.1055 (16) 0.0563 (11) −0.0025 (15) −0.0044 (13) 0.0275 (12)

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N1 0.0509 (12) 0.0484 (11) 0.0463 (11) 0.0052 (10) 0.0029 (10) 0.0042 (9)
N2 0.0614 (15) 0.0707 (16) 0.0731 (16) −0.0068 (14) −0.0072 (13) 0.0266 (13)
C1 0.0431 (14) 0.0477 (12) 0.0463 (12) 0.0035 (11) 0.0067 (11) 0.0043 (10)
C2 0.0454 (15) 0.0529 (13) 0.0482 (12) 0.0020 (12) 0.0069 (11) 0.0015 (11)
C3 0.0515 (16) 0.0504 (13) 0.0628 (15) 0.0051 (12) 0.0070 (12) 0.0082 (11)
C4 0.0660 (19) 0.0615 (16) 0.0596 (16) 0.0045 (15) 0.0068 (14) 0.0193 (13)
C5 0.079 (2) 0.0708 (17) 0.0453 (12) 0.0029 (16) 0.0008 (14) 0.0040 (12)
C6 0.0614 (16) 0.0526 (14) 0.0509 (14) 0.0027 (13) 0.0009 (13) −0.0010 (12)
C7 0.081 (2) 0.0651 (16) 0.0577 (14) −0.0020 (16) 0.0041 (14) −0.0097 (13)
C8 0.105 (3) 0.0539 (15) 0.087 (2) −0.0044 (18) 0.009 (2) 0.0079 (15)
C9 0.0467 (15) 0.0539 (13) 0.0479 (12) 0.0039 (12) 0.0081 (12) 0.0010 (11)
C10 0.0406 (13) 0.0467 (12) 0.0471 (13) 0.0009 (11) 0.0030 (11) 0.0026 (10)
C11 0.0578 (16) 0.0514 (13) 0.0483 (12) 0.0057 (12) 0.0043 (11) −0.0031 (11)
C12 0.0608 (17) 0.0424 (12) 0.0621 (15) 0.0015 (12) 0.0011 (13) 0.0007 (11)
C13 0.0436 (14) 0.0550 (14) 0.0515 (12) −0.0029 (12) −0.0050 (12) 0.0116 (11)
C14 0.0521 (15) 0.0601 (16) 0.0447 (12) 0.0018 (13) −0.0007 (11) 0.0014 (12)
C15 0.0521 (15) 0.0456 (12) 0.0512 (13) 0.0046 (12) 0.0015 (12) 0.0005 (11)

Geometric parameters (Å, °)

O1—N2 1.215 (3) C12—C13 1.368 (3)
O2—N2 1.224 (3) C13—C14 1.365 (3)
N1—C1 1.419 (3) C14—C15 1.376 (3)
N1—C9 1.262 (3) C4—H4 0.9300
N2—C13 1.476 (3) C5—H5 0.9300
C1—C2 1.396 (3) C6—H6 0.9300
C1—C6 1.390 (3) C7—H7A 0.9600
C2—C3 1.401 (3) C7—H7B 0.9600
C2—C7 1.512 (3) C7—H7C 0.9600
C3—C4 1.379 (3) C8—H8A 0.9600
C3—C8 1.502 (3) C8—H8B 0.9600
C4—C5 1.374 (3) C8—H8C 0.9600
C5—C6 1.373 (3) C9—H9 0.9300
C9—C10 1.468 (3) C11—H11 0.9300
C10—C11 1.381 (3) C12—H12 0.9300
C10—C15 1.387 (3) C14—H14 0.9300
C11—C12 1.373 (3) C15—H15 0.9300
C1—N1—C9 120.49 (18) C5—C4—H4 119.00
O1—N2—O2 123.9 (2) C4—C5—H5 120.00
O1—N2—C13 118.2 (2) C6—C5—H5 120.00
O2—N2—C13 118.0 (2) C1—C6—H6 120.00
N1—C1—C2 117.16 (18) C5—C6—H6 120.00
N1—C1—C6 122.56 (19) C2—C7—H7A 109.00
C2—C1—C6 120.2 (2) C2—C7—H7B 109.00
C1—C2—C3 119.2 (2) C2—C7—H7C 109.00
C1—C2—C7 119.7 (2) H7A—C7—H7B 110.00
C3—C2—C7 121.1 (2) H7A—C7—H7C 109.00
C2—C3—C4 118.9 (2) H7B—C7—H7C 109.00
C2—C3—C8 121.1 (2) C3—C8—H8A 109.00

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C4—C3—C8 119.9 (2) C3—C8—H8B 109.00
C3—C4—C5 121.8 (2) C3—C8—H8C 109.00
C4—C5—C6 119.6 (2) H8A—C8—H8B 109.00
C1—C6—C5 120.2 (2) H8A—C8—H8C 109.00
N1—C9—C10 121.6 (2) H8B—C8—H8C 109.00
C9—C10—C11 119.8 (2) N1—C9—H9 119.00
C9—C10—C15 121.1 (2) C10—C9—H9 119.00
C11—C10—C15 119.1 (2) C10—C11—H11 120.00
C10—C11—C12 120.7 (2) C12—C11—H11 120.00
C11—C12—C13 118.7 (2) C11—C12—H12 121.00
N2—C13—C12 118.7 (2) C13—C12—H12 121.00
N2—C13—C14 118.9 (2) C13—C14—H14 121.00
C12—C13—C14 122.4 (2) C15—C14—H14 121.00
C13—C14—C15 118.6 (2) C10—C15—H15 120.00
C10—C15—C14 120.6 (2) C14—C15—H15 120.00
C3—C4—H4 119.00
C9—N1—C1—C2 −153.3 (2) C2—C3—C4—C5 0.2 (4)
C9—N1—C1—C6 30.1 (4) C8—C3—C4—C5 −179.1 (3)
C1—N1—C9—C10 −178.4 (2) C3—C4—C5—C6 0.1 (4)
O1—N2—C13—C12 −9.2 (3) C4—C5—C6—C1 −1.3 (4)
O1—N2—C13—C14 171.7 (2) N1—C9—C10—C11 176.3 (2)
O2—N2—C13—C12 170.3 (3) N1—C9—C10—C15 −5.4 (4)
O2—N2—C13—C14 −8.8 (3) C9—C10—C11—C12 178.5 (2)
N1—C1—C2—C3 −178.7 (2) C15—C10—C11—C12 0.1 (3)
N1—C1—C2—C7 2.6 (3) C9—C10—C15—C14 −178.2 (2)
C6—C1—C2—C3 −2.0 (3) C11—C10—C15—C14 0.2 (3)
C6—C1—C2—C7 179.3 (2) C10—C11—C12—C13 −0.5 (4)
N1—C1—C6—C5 178.8 (2) C11—C12—C13—N2 −178.3 (2)
C2—C1—C6—C5 2.3 (4) C11—C12—C13—C14 0.8 (4)
C1—C2—C3—C4 0.8 (4) N2—C13—C14—C15 178.6 (2)
C1—C2—C3—C8 −180.0 (3) C12—C13—C14—C15 −0.5 (3)
C7—C2—C3—C4 179.4 (2) C13—C14—C15—C10 0.0 (3)
C7—C2—C3—C8 −1.3 (4)

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Fig. 1

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